CN108504175A - A kind of alcohol water-base gravure composite inks for plastics and preparation method thereof - Google Patents
A kind of alcohol water-base gravure composite inks for plastics and preparation method thereof Download PDFInfo
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- CN108504175A CN108504175A CN201810377223.8A CN201810377223A CN108504175A CN 108504175 A CN108504175 A CN 108504175A CN 201810377223 A CN201810377223 A CN 201810377223A CN 108504175 A CN108504175 A CN 108504175A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention provides a kind of alcohol water-base gravure composite inks for plastics comprising the component based on quality parts ratio below：35 48 parts of polyurethane-modified acrylic acid lotion；0.5 2 parts of high-molecular type dispersing agent；0.2 1 parts of aqueous polyethylene wax；0.5 1 parts of aerosil；10 38 parts of pigment powder；0.5 2 parts of triethanolamine；4.9 20 parts of 12 29 parts of ethyl alcohol and deionized water.The present invention is blocked using low-boiling organic amine, introducing low boiling point organic amine, and under room temperature, low-boiling amine volatilization is slow, still has a large amount of hydrophilic radical in resin, has preferable dissolubility in alcohol-water system；When ink, which is made, in resin printed baking oven, low-boiling amine can accelerate to escape on resin, resin hydrophilic radical is caused to largely reduce, moisture evaporation is accelerated, it is water-fast after ink dries, and the ink on printing plate is still room temperature, still there is a large amount of hydrophilic radical, still there is good solubility whithin a period of time, meet printing requirement.
Description
Technical field
The present invention relates to the preparation methods of a kind of resin of alcohol water-base gravure composite inks for plastics and its ink, belong to ink
Technical field.
Background technology
With the promotion of human living standard, demand of the people to packaging be more and more diversified, fining, quality and ring
Guarantorization, incident to be people have higher requirement to assigning packaging with the ink of fresh and alive vitality --- " green oil
Ink ".
From 1 day October in 2015,《Volatile organic matter Pollution Charges Site method》It is formal to implement, packages printing industry name
Row are wherein；From 1 day January in 2016,《The Law of the People's Republic of China on the Prevention and Control of Atmospheric Pollution》(revised edition) is formally implemented, and volatility has
Machine object (VOCs) is discharged is included in supervision with improvement.End the end of last year, Beijing, Shanghai City, Jiangsu Province, Anhui Province, Hunan Province, four
Chuan Sheng, Tianjin, Liaoning Province, Hubei Province etc. levy volatile organic matter VOCs charges for disposing pollutants.Shanghai City, which is distinctly claimed, passes through collection
VOCs charges for disposing pollutants, to 50% or more emission reduction in 2017.Traditional solvent-based ink will produce largely in actual application
VOCs, this will cause the use cost of printing house to rise.Ink is molten from benzophenone, ester is molten, the molten equal solvent type ink of ester alcohol is to water
Soluble ink development is imperative.
As VOCs charges for disposing pollutants, the side that low VOCs or even Diamond Search s make great efforts at novel environment friendly ink are imposed in national legislation
To.
Diamond Search s：All use water replace traditional benzene, ketone, ester, alcohol equal solvent as water-based ink solvent be the most
Ideal Diamond Search s environment-friendly inks, but current, the ink for all using water to be prepared as solvent, the print speed printing speed of ink slowly (water compared with
The rate of volatilization of solvent is low), printing effect is poor compared with solvent type, and drying energy consumption is big (about 1.3-1.5 times of solvent inkjet ink), and the country is existing
Some printing equipments cannot be satisfied requirement, and the wish of the printing equipment of Packaging and Printing Enterprises replacement in a short time is little, these will all lead
Cause water-based ink that can not still replace traditional solvent-borne ink in a short time.
Low VOCs：Lower alcohol has preferable compatibility with water, is arranged in pairs or groups using alcohol and water as solvent, can be to a certain extent
Overcome the rate of volatilization of water small, the problems such as surface tension is big, while also can utmostly reduce the discharge of VOCs.Using ethyl alcohol,
The rudimentary alcohol and water such as isopropanol does the alcohol aqueous composite ink of solvent preparation, the print speed printing speed of ink compared with solvent-based ink under
Drop still can reach the requirement of most printing houses, and the printability of ink is close to solvent-based ink, and practical application is without apparent poor
Away from color developing is much better than water-based ink.In a short time, it in the case where being not required to adjust existing printing equipment, is expected to substitute traditional molten
Based ink.
Under the background that the water-based compound oil ink of Diamond Search s can not replace traditional solvent-borne ink in a short time, low VOCs's
Alcohol aqueous composite ink is replacement traditional solvent-borne one more environmentally friendly selection of ink in a short time, and by traditional solvent-borne oil
Ink meets the incremental development trend of ink to the one fabulous transition selection of water-based ink.
Currently, alcohol aqueous composite ink has that solubility and water resistance are difficult and and obtain, the solvable system ink of alkali
Solubility is good, meanwhile, water resistance is very poor, and water-soluble acrylic/polyurethane system can reach preferable water resistance by self-crosslinking,
And ink solubility is not satisfactory.
Invention content：
The purpose of the present invention for alcohol aqueous composite ink there are problems that water resistance and solubility be difficult to and and obtain, carry
For a kind of low boiling point organic amine blocked polyurethane modified acrylic acid emulsion, and prepare by it that water resistance is good, solubility is good, dry
Dry fast alcohol water-base gravure composite inks for plastics.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of alcohol water-base gravure composite inks for plastics comprising the component based on quality parts ratio below：
The polyurethane-modified acrylic acid lotion includes the following component based on quality parts ratio：
The preparation method of the alcohol water-base gravure composite inks for plastics is：
1. weighing 16-22 parts of polyurethane-modified acrylic acid lotion, 0.5-2 parts of high-molecular type dispersing agent, 0.2-1 successively
The aqueous polyethylene wax of part, 0.5-1 parts of aerosils, 10-38 parts of pigment powder, 0.5-1 parts of triethanolamines, solvent 11-30
Part, dispersion, 1200r/min disperses 30min, and the solvent is the mixture of ethyl alcohol and deionized water, the mixed proportion of the two
For：Ethyl alcohol：Deionized water=1.5:1-2.5:1；
2. finely dispersed material is crossed sand mill to be sanded, 45-55 DEG C of temperature, flow 2L/min is sanded in control, until grinding
Grinding rate qualification (chalk≤20 μm, color ink≤15 μm)；
3. the qualified material of grinding is added in dispersion thereto 19-26 parts polyurethane-modified acrylic acid lotion,
3-19 parts of 0.5-1 parts of triethanolamines, solvent continue to disperse 15-20min, obtain alcohol water-base gravure composite inks for plastics, wherein
The solvent is the mixture of ethyl alcohol and deionized water, and the mixed proportion of the two is：Ethyl alcohol：Deionized water=1.5:1-2.5:1.
Wherein, the synthetic method of the polyurethane-modified acrylic acid lotion is：
1. the hydroxypropyl acrylate of formula ratio, dihydromethyl propionic acid (DMPA), polyester diol (molecular weight 500) are depressurized
Dehydration, for use；
2. four-hole boiling flask is added in dewatered hydroxypropyl acrylate, acrylic acid, methyl methacrylate, it is warming up to 60-
65 DEG C, the acetone soln dissolved with azodiisobutyronitrile (AIBN) is slowly added dropwise, after being added dropwise, it is small to continue insulation reaction 2.5-3
When, dewatered dihydromethyl propionic acid (DMPA), polyester diol (molecular weight 500) is added, reacts 1.5-2 hours；
3. being warming up to 85-90 DEG C, it is passed through nitrogen, instills the tetramethyl two for being mixed with dibutyl tin laurate (DBT) dropwise
Methylene diisocyanate (TMXDI), after being added dropwise, the reaction was continued 2-3 hours, and a small amount of acetone regulation system viscosity is added,
Primary every 30 minutes measurement-NCO groups, when measurement-NCO group no longer changes, being cooled to 35-40 DEG C of addition low boiling point has
Machine amine neutralizes, and is subsequently added into deionized water, high speed dispersion emulsification pretreatment 30 minutes, and vacuum distillation removes acetone, adjusts PH=7-
9 obtain polyurethane-modified acrylic acid lotion.
Preferably, the low boiling point organic amine be ethylenediamine, n-butylamine, diisopropylamine, cyclohexylamine, 1,2- propane diamine,
Above one or several kinds of mixtures.
Compared to the prior art, the beneficial effects of the present invention are：
The present invention is blocked using low-boiling organic amine, introducing low boiling point organic amine, and under room temperature, low-boiling amine volatilization is slow,
Still there is a large amount of hydrophilic radical in resin, has preferable dissolubility in alcohol-water system；When ink, which is made, in resin printed baking oven,
Low-boiling amine can accelerate to escape on resin, and resin hydrophilic radical is caused to largely reduce, and moisture evaporation is accelerated, resistance to after ink dries
Water, and the ink on printing plate is still room temperature, still there is a large amount of hydrophilic radical, still has good redissolution whithin a period of time
Property, meet printing requirement.Select the ethyl alcohol inside lower alcohol as solvent simultaneously, not only expense is low, small toxicity, phase
Consumer is easier to than other alcohol to be received.
Specific implementation mode
Embodiment 1
1. hydroxypropyl acrylate, dihydromethyl propionic acid (DMPA) and polyester diol (molecular weight 500) decompression dehydration；
2. dewatered 26.7g hydroxypropyl acrylates, 14.8g acrylic acid, 18.0g methyl methacrylates are added four mouthfuls
In flask, 62 DEG C are warming up to, the acetone soln dissolved with 4.9g azodiisobutyronitriles (AIBN) is slowly added dropwise, after being added dropwise, after
Continuous insulation reaction 2.5 hours, is added dewatered 8.7g dihydromethyl propionic acids (DMPA), 102.5g polyester diol (molecular weight
500) it, reacts 1.5 hours；
3. being warming up to 85 DEG C, it is passed through nitrogen, instills the tetramethyl two for being mixed with two drop dibutyl tin laurates (DBT) dropwise
Methylene diisocyanate (TMXDI) 37.8g, after being added dropwise, the reaction was continued 2.5 hours, and a small amount of acetone regulation system is added
Viscosity, it is primary every 30 minutes measurement-NCO groups, when measurement-NCO group no longer changes, it is cooled to 35 DEG C of addition 10.5g
Ethylenediamine neutralizes, and is subsequently added into 328.5 deionized waters, high speed dispersion emulsification pretreatment 30 minutes, and vacuum distillation removes acetone, adjusts
Section PH=7-9 obtains polyurethane-modified acrylic acid lotion.
4. weighing 20 parts of polyurethane-modified acrylic acid lotion, 0.5 part of high-molecular type dispersing agent, 0.5 part of water successively
Property polyethylene wax, 0.5 part of aerosil, 38 parts of rutile type titanium whites, solvent (ethyl alcohol：Deionized water=2.5:1)13
Part, dispersion, 1200r/min disperses 30min；
5. finely dispersed material is crossed sand mill to be sanded, 50 ± 5 DEG C, flow 2L/min of temperature is sanded in control, until grinding
Grinding rate is qualified；
6. the qualified material of grinding to be added to 23 parts of polyurethane-modified acrylic acid lotion, 0.5 part of three ethyl alcohol when disperseing
Amine, solvent (ethyl alcohol：Deionized water=2.5:1) 4 parts, continue to disperse 20min to get to alcohol water-based plastic gravure composite printing ink,
That is chalk.
Embodiment 2
1. hydroxypropyl acrylate, dihydromethyl propionic acid (DMPA), polyester diol (molecular weight 500) decompression dehydration；
2. dewatered 30.6g hydroxypropyl acrylates, 16.9g acrylic acid, 20.3g methyl methacrylates are added four mouthfuls
Flask is warming up to 60 DEG C, and the acetone soln dissolved with 5.4g azodiisobutyronitriles (AIBN) is slowly added dropwise, and after being added dropwise, continues
Dewatered 9.7g dihydromethyl propionic acids (DMPA), 117.5g polyester diols (molecular weight 500) is added in insulation reaction 3 hours,
Reaction 1.5 hours；
3. being warming up to 90 DEG C, it is passed through nitrogen, instills the tetramethyl two for being mixed with two drop dibutyl tin laurates (DBT) dropwise
Methylene diisocyanate (TMXDI) 41.5g, after being added dropwise, the reaction was continued 3 hours, and it is viscous that a small amount of acetone regulation system is added
Degree, it is primary every 30 minutes measurement-NCO groups, when measurement-NCO group no longer changes, it is cooled to 35 DEG C of addition 12.8g second
Diamines and 1,2- propane diamine press 1:1 mixing neutralizes, and is subsequently added into 374.0g deionized waters, high speed dispersion emulsification pretreatment 30 minutes,
Vacuum distillation removes acetone, adjusts PH=7-9 and obtains polyurethane-modified acrylic acid lotion.
4. weigh 18 parts of polyurethane-modified acrylic acid lotion successively, 1 part of high-molecular type dispersing agent, 0.3 part aqueous
Polyethylene wax, 0.5 part of aerosil, 13 parts of 14# Huangs, 0.5 part of triethanolamine, solvent (ethyl alcohol：Deionized water=1.5:1)
30 parts, dispersion, 1200r/min disperses 30min；
5. finely dispersed material is crossed sand mill to be sanded, 50 ± 5 DEG C, flow 2L/min of temperature is sanded in control, until grinding
Grinding rate is qualified；
6. the qualified material of grinding to be added to 23 parts of polyurethane-modified acrylic acid lotion, 0.5 part of three ethyl alcohol when disperseing
Amine, solvent (ethyl alcohol：Deionized water=1.5:1) 13.2 parts, continue to disperse 15min to get to alcohol water-based plastic gravure composite printing
Ink, i.e., yellow ink.
Embodiment 3
1. hydroxypropyl acrylate, dihydromethyl propionic acid (DMPA), polyester diol (molecular weight 500) decompression dehydration；
2. dewatered 33.2g hydroxypropyl acrylates, 18.4g acrylic acid, 21.7g methyl methacrylates are added four mouthfuls
Flask is warming up to 60 DEG C, and the acetone soln dissolved with 5.9g azodiisobutyronitriles (AIBN) is slowly added dropwise, and after being added dropwise, continues
Dewatered 11.1g dihydromethyl propionic acids (DMPA), 127.5g polyester diol (molecular weight is added in insulation reaction 2.5 hours
500) it, reacts 2 hours；
3. being warming up to 85 DEG C, it is passed through nitrogen, instills the tetramethyl two for being mixed with two drop dibutyl tin laurates (DBT) dropwise
Methylene diisocyanate (TMXDI) 45.4g, after being added dropwise, the reaction was continued 3 hours, and it is viscous that a small amount of acetone regulation system is added
Degree, it is primary every 30 minutes measurement-NCO groups, when measurement-NCO group no longer changes, it is cooled to 35 DEG C of addition 21.5g bis-
Isopropylamine neutralizes, and is subsequently added into 418.2 deionized waters, high speed dispersion emulsification pretreatment 30 minutes, and vacuum distillation removes acetone, adjusts
Section PH=7-9 obtains polyurethane-modified acrylic acid lotion.
4. weigh 19 parts of polyurethane-modified acrylic acid lotion successively, 2 parts of high-molecular type dispersing agent, 1 part aqueous poly-
Ethylene waxes, 0.5 part of aerosil, 15 parts of 146# are red, 1 part of triethanolamine, solvent (ethyl alcohol：Deionized water=2:1)22.5
Part, dispersion, 1200r/min disperses 30min；
5. finely dispersed material is crossed sand mill to be sanded, 50 ± 5 DEG C, flow 2L/min of temperature is sanded in control, until grinding
Grinding rate is qualified；
6. the qualified material of grinding is added to 24 parts of polyurethane-modified acrylic acid lotion when disperseing, 1 part of triethanolamine,
Solvent (ethyl alcohol：Deionized water=2:1) 14 parts, continue to disperse 15min to get to alcohol water-based plastic gravure composite printing ink, i.e., it is red
Ink.
Embodiment 4
1. hydroxypropyl acrylate, dihydromethyl propionic acid (DMPA), polyester diol (molecular weight 500) decompression dehydration；
2. dewatered 37.7g hydroxypropyl acrylates, 20.9g acrylic acid, 23.1g methyl methacrylates are added four mouthfuls
Flask is warming up to 60 DEG C, and the acetone soln dissolved with 6.4g azodiisobutyronitriles (AIBN) is slowly added dropwise, and after being added dropwise, continues
Dewatered 12.2g dihydromethyl propionic acids (DMPA), 145g polyester diols (molecular weight 500) is added in insulation reaction 2 hours,
Reaction 2 hours；
3. being warming up to 85 DEG C, it is passed through nitrogen, instills the tetramethyl for being mixed with two drop g dibutyl tin laurates (DBT) dropwise
Dimethylene diisocyanate (TMXDI) 49.0g, after being added dropwise, the reaction was continued 3 hours, and a small amount of acetone regulation system is added
Viscosity, it is primary every 30 minutes measurement-NCO groups, when measurement-NCO group no longer changes, it is cooled to 40 DEG C of addition 23.3g
Cyclohexylamine neutralizes, and is subsequently added into 466.8 parts of deionized waters, high speed dispersion emulsification pretreatment 30 minutes, and vacuum distillation removes acetone,
It adjusts PH=7-9 and obtains polyurethane-modified acrylic acid lotion.
4. weigh 22 parts of polyurethane-modified acrylic acid lotion successively, 1 part of high-molecular type dispersing agent, 0.3 part aqueous
Polyethylene wax, 0.5 part of aerosil, 15 part 15:3 phthalocyanine blues, 1 part of triethanolamine, solvent (ethyl alcohol：Deionized water=2:
1) 22 parts, dispersion, 1200r/min disperses 30min；
5. finely dispersed material is crossed sand mill to be sanded, 50 ± 5 DEG C, flow 2L/min of temperature is sanded in control, until grinding
Grinding rate is qualified；
6. the qualified material of grinding is added to 26 parts of polyurethane-modified acrylic acid lotion when disperseing, 1 part of triethanolamine,
Solvent (ethyl alcohol：Deionized water=2:1) 11.2 parts, continue to disperse 15min to get to alcohol water-based plastic gravure composite printing ink, i.e.,
Lan Mo.
Embodiment 5
1. hydroxypropyl acrylate, dihydromethyl propionic acid (DMPA), polyester diol (molecular weight 500) decompression dehydration；
2. dewatered 40.3g hydroxypropyl acrylates, 22.3g acrylic acid, 25.3g methyl methacrylates are added four mouthfuls
Flask is warming up to 60 DEG C, and the acetone soln dissolved with 6.9g azodiisobutyronitriles (AIBN) is slowly added dropwise, and after being added dropwise, continues
Dewatered 12.9g dihydromethyl propionic acids (DMPA), 155g polyester diols (molecular weight 500) is added in insulation reaction 3 hours,
Reaction 1.5 hours；
3. being warming up to 90 DEG C, it is passed through nitrogen, instills the tetramethyl two for being mixed with three drop dibutyl tin laurates (DBT) dropwise
Methylene diisocyanate (TMXDI) 53.2g, after being added dropwise, the reaction was continued 3 hours, and it is viscous that a small amount of acetone regulation system is added
Degree, it is primary every 30 minutes measurement-NCO groups, when measurement-NCO group no longer changes, 35 DEG C of addition 19.1g 1 are cooled to,
2- propane diamine neutralizes, and is subsequently added into 492.2g deionized waters, high speed dispersion emulsification pretreatment 30 minutes, and vacuum distillation removes acetone,
It adjusts PH=7-9 and obtains polyurethane-modified acrylic acid lotion.
4. weighing 21.5 parts of polyurethane-modified acrylic acid lotion, 0.5 part of high-molecular type dispersing agent, 1 part of water successively
Property polyethylene wax, 0.5 part of aerosil, 15 parts of carbon blacks, 1 part of triethanolamine, solvent (ethyl alcohol：Deionized water=2:1)23
Part, dispersion, 1200r/min disperses 30min；
5. finely dispersed material is crossed sand mill to be sanded, 50 ± 5 DEG C, flow 2L/min of temperature is sanded in control, until grinding
Grinding rate is qualified；
6. the qualified material of grinding to be added to 24.5 parts of polyurethane-modified acrylic acid lotion, 1 part of three ethyl alcohol when disperseing
Amine, solvent (ethyl alcohol：Deionized water=2:1) 12 parts, continue to disperse 15min to get to alcohol water-based plastic gravure composite printing ink, i.e.,
Tusche.
Embodiment 6
1. hydroxypropyl acrylate, dihydromethyl propionic acid (DMPA), polyester diol (molecular weight 500) decompression dehydration；
2. dewatered 33.2g hydroxypropyl acrylates, 18.4g acrylic acid, 21.7g methyl methacrylates are added four mouthfuls
Flask is warming up to 60 DEG C, and the acetone soln dissolved with 5.9g azodiisobutyronitriles (AIBN) is slowly added dropwise, and after being added dropwise, continues
Dewatered 11.1g dihydromethyl propionic acids (DMPA), 127.5g polyester diol (molecular weight is added in insulation reaction 2.5 hours
500) it, reacts 2 hours；
3. being warming up to 85 DEG C, it is passed through nitrogen, instills the tetramethyl two for being mixed with two drop dibutyl tin laurates (DBT) dropwise
Methylene diisocyanate (TMXDI) 45.4g, after being added dropwise, the reaction was continued 3 hours, and it is viscous that a small amount of acetone regulation system is added
Degree, it is primary every 30 minutes measurement-NCO groups, when measurement-NCO group no longer changes, it is cooled to 35 DEG C of addition 21.1g rings
Hexylamine neutralizes, and is subsequently added into 417.6 deionized waters, high speed dispersion emulsification pretreatment 30 minutes, and vacuum distillation removes acetone, adjusts
PH=7-9 obtains polyurethane-modified acrylic acid lotion.
4. weighing 20 parts of polyurethane-modified acrylic acid lotion, 1.5 parts of high-molecular type dispersing agent, 0.5 part of water successively
Property polyethylene wax, 1 part of aerosil, 15 parts of 146# are red, 0.5 part of triethanolamine, solvent (ethyl alcohol：Deionized water=2:1)
25 parts, dispersion, 1200r/min disperses 30min；
5. finely dispersed material is crossed sand mill to be sanded, 50 ± 5 DEG C, flow 2L/min of temperature is sanded in control, until grinding
Grinding rate is qualified；
6. the qualified material of grinding to be added to 24 parts of polyurethane-modified acrylic acid lotion, 0.5 part of three ethyl alcohol when disperseing
Amine, solvent (ethyl alcohol：Deionized water=2:1) 12 parts, continue to disperse 15min to get to alcohol water-based plastic gravure composite printing ink,
For red ink.
Embodiment 7
1. hydroxypropyl acrylate, dihydromethyl propionic acid (DMPA), polyester diol (molecular weight 500) decompression dehydration；
2. dewatered 26.7g hydroxypropyl acrylates, 14.8g acrylic acid, 18.0g methyl methacrylates are added four mouthfuls
Flask is warming up to 62 DEG C, and the acetone soln dissolved with 4.9g azodiisobutyronitriles (AIBN) is slowly added dropwise, and after being added dropwise, continues
Dewatered 8.7g dihydromethyl propionic acids (DMPA), 102.5g polyester diol (molecular weight is added in insulation reaction 2.5 hours
500) it, reacts 1.5 hours；
3. being warming up to 85 DEG C, it is passed through nitrogen, instills the tetramethyl two for being mixed with two drop dibutyl tin laurates (DBT) dropwise
Methylene diisocyanate (TMXDI) 37.8g, after being added dropwise, the reaction was continued 2.5 hours, and a small amount of acetone regulation system is added
Viscosity, it is primary every 30 minutes measurement-NCO groups, when measurement-NCO group no longer changes, it is cooled to 35 DEG C of addition 17.4g
Cyclohexylamine neutralizes, and is subsequently added into 338.9 deionized waters, high speed dispersion emulsification pretreatment 30 minutes, and vacuum distillation removes acetone, adjusts
Section PH=7-9 obtains polyurethane-modified acrylic acid lotion.
4. weigh 18 parts of polyurethane-modified acrylic acid lotion successively, 1 part of high-molecular type dispersing agent, 0.6 part aqueous
Polyethylene wax, 0.5 part of aerosil, 13 parts of 14# Huangs, 0.5 part of triethanolamine, solvent (ethyl alcohol：Deionized water=1.5:1)
25 parts, dispersion, 1200r/min disperses 30min；
5. finely dispersed material is crossed sand mill to be sanded, 50 ± 5 DEG C, flow 2L/min of temperature is sanded in control, until grinding
Grinding rate is qualified；
6. the qualified material of grinding is added to 25 parts of polyurethane-modified acrylic acid lotion when disperseing, 1 part of triethanolamine,
Solvent (ethyl alcohol：Deionized water=1.5:1) 15.4 parts, continue to disperse 20min to get to alcohol water-based plastic gravure composite printing ink
(Huang Mo).
Embodiment 8
1. hydroxypropyl acrylate, dihydromethyl propionic acid (DMPA), polyester diol (molecular weight 500) decompression dehydration；
2. dewatered 37.7g hydroxypropyl acrylates, 20.9g acrylic acid, 23.1g methyl methacrylates are added four mouthfuls
Flask is warming up to 60 DEG C, and the acetone soln dissolved with 6.4g azodiisobutyronitriles (AIBN) is slowly added dropwise, and after being added dropwise, continues
Dewatered 12.2g dihydromethyl propionic acids (DMPA), 145g polyester diols (molecular weight 500) is added in insulation reaction 2 hours,
Reaction 2 hours；
3. being warming up to 85 DEG C, it is passed through nitrogen, instills the tetramethyl for being mixed with two drop g dibutyl tin laurates (DBT) dropwise
Dimethylene diisocyanate (TMXDI) 49.0g, after being added dropwise, the reaction was continued 3 hours, and a small amount of acetone regulation system is added
Viscosity, it is primary every 30 minutes measurement-NCO groups, when measurement-NCO group no longer changes, it is cooled to 40 DEG C of addition 14.1g
Ethylenediamine neutralizes, and is subsequently added into 453.0 parts of deionized waters, high speed dispersion emulsification pretreatment 30 minutes, and vacuum distillation removes acetone,
It adjusts PH=7-9 and obtains polyurethane-modified acrylic acid lotion.
4. weighing 20 parts of polyurethane-modified acrylic acid lotion, 1.5 parts of high-molecular type dispersing agent, 0.6 part of water successively
Property polyethylene wax, 0.7 part of aerosil, 13 part 15:3 phthalocyanine blues, 0.5 part of triethanolamine, solvent (ethyl alcohol：Deionized water
=2:1) 25 parts, dispersion, 1200r/min disperses 30min；
5. finely dispersed material is crossed sand mill to be sanded, 50 ± 5 DEG C, flow 2L/min of temperature is sanded in control, until grinding
Grinding rate is qualified；
6. the qualified material of grinding to be added to 24 parts of polyurethane-modified acrylic acid lotion, 0.5 part of three ethyl alcohol when disperseing
Amine, solvent (ethyl alcohol：Deionized water=2:1) 14.2 parts, continue to disperse 15min to get to alcohol water-based plastic gravure composite printing ink
(Lan Mo).
The component composition such as following table of alcohol water-based plastic gravure composite printing ink quality parts ratio made from the above various embodiments：
| Constituent/ratio (part) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Polyurethane-modified acrylic acid lotion | 43 | 41 | 43 | 48 | 46 | 44 | 43 | 44 |
| High-molecular type dispersing agent | 0.5 | 1 | 2 | 1 | 0.5 | 1.5 | 1 | 1.5 |
| Aqueous polyethylene wax | 0.5 | 0.3 | 1 | 0.3 | 1 | 0.5 | 0.6 | 0.6 |
| Aerosil | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 1 | 0.5 | 0.7 |
| Corresponding toner | 38 | 13 | 15 | 15 | 15 | 15 | 13 | 13 |
| Triethanolamine | 0.5 | 1 | 2 | 2 | 2 | 1 | 1.5 | 1 |
| Ethyl alcohol | 12.1 | 25.9 | 24.3 | 22.1 | 23.3 | 24.7 | 24.2 | 26.1 |
| Deionized water | 4.9 | 17.3 | 12.2 | 11.1 | 11.7 | 12.3 | 16.2 | 13.1 |
Printing house's test-run a machine is sent by alcohol water-based plastic gravure composite printing ink made from the above various embodiments, it is existing not adjusting
Under equipment, print speed printing speed is up to 160-180m/min, the key technical indexes such as following table：
Remarks：With reference to GB/T 26394-2011, QB/T2024-2012 standard testings
As can be seen from the above table, the present invention introduces low boiling point organic amine sealing end, at salt by polyurethane-modified acrylic acid, can
The water resistance and solubility of alcohol aqueous composite ink effectively have been taken into account, while having also improved the rate of drying of ink.Under room temperature, tree
Fat has preferable water solubility, ink is made, when printing baking oven, low-boiling amine quickly escapes, and in the short time, hydrophilic radical is big
Amount is reduced, system hydrophobic, and water escapes speed and increases, and accelerates drying, tentatively has water resistance after ink dries, as resin is selfed
Connection reaction, the water resistance and adhesive force of ink are all further promoted；Ink on printing plate does not cross hot wind, low boiling in resin
Point amine volatilization is slower, and whole system is still in hydrophily, and ink still has preferable alcohol-soluble and water-soluble, that is, has preferable solubility.
Claims (6)
1. a kind of alcohol water-base gravure composite inks for plastics, it is characterised in that：It includes the following component based on quality parts ratio：
2. alcohol water-base gravure composite inks for plastics according to claim 1, it is characterised in that：The polyurethane-modified propylene
Yogurt liquid includes the following component based on quality parts ratio：
3. alcohol water-base gravure composite inks for plastics according to claim 2, it is characterised in that：The low boiling point organic amine
For one or several kinds of mixtures in ethylenediamine, n-butylamine, diisopropylamine, cyclohexylamine and 1,2- propane diamine.
4. a kind of preparation method of alcohol water-base gravure composite inks for plastics described in claim 1, it is characterised in that：It include with
Lower step：
S1, the polyurethane-modified acrylic acid lotion for weighing 16-22 parts successively, 0.5-2 parts of high-molecular type dispersing agent, 0.2-1 parts
Aqueous polyethylene wax, 0.5-1 parts of aerosils, 10-38 parts of pigment powder, 0.5-1 parts of triethanolamines, 11-30 parts of solvent,
Disperseed with rotating speed 1200r/min, disperse duration 30min, the solvent is the mixture of ethyl alcohol and deionized water, the mixing of the two
Ratio is：Ethyl alcohol：Deionized water=1.5:1-2.5:1；
S2, finely dispersed material is crossed to sand mill sand milling, 45-55 DEG C of temperature, flow 2L/min is sanded in control, until grinding is thin
Degree is qualified；
S3, polyurethane-modified acrylic acid lotion, the 0.5-1 that the qualified material of grinding is added to 19-26 parts thereto when disperseing
Part triethanolamine, 3-19 parts of solvent continue to disperse 15-20min, obtain alcohol water-base gravure composite inks for plastics, wherein described molten
Agent is the mixture of ethyl alcohol and deionized water, and the mixed proportion of the two is：Ethyl alcohol：Deionized water=1.5:1-2.5:1.
5. according to the method described in claim 4, it is characterized in that：In the S2, the standard of the fineness of grind qualification is：In vain
Ink≤20 μm, color ink≤15 μm.
6. a kind of synthetic method for the polyurethane-modified acrylic acid lotion being used to prepare described in claim 2, which is characterized in that its
Include the following steps：
S11, by the hydroxypropyl acrylate of formula ratio, dihydromethyl propionic acid, polyester diol decompression dehydration, for use；
S22, four-hole boiling flask is added in dewatered hydroxypropyl acrylate, acrylic acid, methyl methacrylate, is warming up to 60-65
DEG C, the acetone soln dissolved with azodiisobutyronitrile is slowly added dropwise, after being added dropwise, continues insulation reaction 2.5-3 hours, is added de-
Dihydromethyl propionic acid, polyester diol after water react 1.5-2 hours；
S33, it is warming up to 85-90 DEG C, is passed through nitrogen, instill the tetramethyl dimethylene two for being mixed with dibutyl tin laurate dropwise
Isocyanates, after being added dropwise, the reaction was continued 2-3 hours, and a small amount of acetone regulation system viscosity is added, measured every 30 minutes-
NCO group is primary, when measurement-NCO group no longer changes, is cooled to 35-40 DEG C and the neutralization of low boiling point organic amine is added, then add
Enter deionized water, high speed dispersion emulsification pretreatment 30 minutes, vacuum distillation removes acetone, and adjusting PH=7-9 obtains polyurethane-modified
Acrylic emulsion.
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| CN111154329A (en) * | 2019-12-23 | 2020-05-15 | 广东东方一哥新材料股份有限公司 | Waterborne gravure grindable resin and preparation method thereof |
| WO2021109086A1 (en) * | 2019-12-05 | 2021-06-10 | 惠州德斯坤化工有限公司 | Water-based plastic gravure ink and preparation method therefor |
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